Preparation of sulphonic derivatives



5 Patented Apr. 1,

PREPARATION OF SULPHONIC DERIVATIVES Morris B. Katzrnan, Chicago, 111.,assignor to The Emulsol Corporation, Chicago, Ill., 1:. corporation ofIllinois No Drawing. Application December 14,1939, 561181 No. 309,162

25 Claims.

. My invention relates to novel methods of preparing certain chemicalcompounds, particularly sulphonic derivatives and intermediates whichare employed in the preparation of said sulphonic derivatives.

In my copending application, Serial No. 219,358,

filed July 15. 1938, now Patent No. 2,184,770, is-

sued December 26, 1939,'I have disclosed the preparation of novelsulphonic compounds most of whichfall within the scope of the generalformula RO-( elk-NY) m--COZ (-SOaM) w I wherein R is an organic radicalcontaining at least four carbon atoms, alk stands for hydrocarbon, forexample, alkylene, or arylene, such 'as ethylene or phenylene, ,Y ishydrogen, alkyl, cy cloalkyl, aikoxyl, aralkyl, aryl, or alkylol, Z ispreferably a hydrocarbon residue, containing preferably less than sixcarbon atoms, M is a cation. and m and w are whole numbers, preferablyfrom one to four.

A more limited aspect of the compounds disclosed in said copendingapplication is represented by the general formula wherein R is ahydrocarbon radical or substituted hydrocarbon radical containing atleast seven and preferably from eleven to seventeen carbon atoms, and Mis a cation. Especially useful compounds are those'wherein is the acylradical derived from a fatty acid contalning upwards of ten carbon atomsto about eighteen carbon atoms, and wherein M is an alkali metal,ammonium, and particularly an ethanolamine cation.

In accordance with the methods specifically described in said copendingapplication for producing the novel compounds disclosed therein, thereaction to produce the intermediate amide, for example, by reactingethyl chloroacetate with an excess of monoethanolamine. was carried outin an aqueous medium. In order toremove the excess of monoethanolamlne.oxalic acid was employed, the oxalic acidforming a precipitate with themonoethanolamirie, namely, monoethanolamine oxalate.- The water was thenremoved by evaporation, the monoethanolamlne oxalate was filtered oil,and the ethyl alcohol which formed during the reaction was distilled oflunder vacuum. The resulting N-beta-hydroxyethyl, chloracetamidewas thenreacted with a carboxylic acyl halide having at least four andparticularly from eight to eighteen carbon atoms to produce an ester,and the resulting ester was then reacted with an alkali sulphite toreplace the chlorine of the chloracet amide radical with a sulphonic,

group.

While the method described hereinabove, and

more particularly in my aforementioned copending application, is quitesatisfactory, I have found that material improvements may be made inproducing the novel sulphonic compounds which I have disclosed in saidcopending application as well as in the preparation of certainintermediates which are utilized in the preparation of said sulphoniccompounds. In general, the improved methods of the present inventionresult in materially higher yields of the desired intermediate amideproducts, easier removal of such unreacted alcohol primary or secondaryamines or, in other words, alcohol or alkylol, nontertiary amines, asmay be present, greater speed of reaction, and the like, the novelprocedures contributing as a whole to the production of the desiredultimate products in a more eflicacious manner and at substantiallylower costs.

In general, the features of my present process involve the carrying outof the reaction of the alcohol ester of the halogeno-carboxylic acid orthe like with the mon'o-ethanolamine or other alkylol'non-tertiary aminein a non-aqueous medium. By a non-aqueous medium, I mean one I which issubstantially devoid of water. Thusyfor example, only the two reactantsmay be present or one of them may be in excess in which case it may beregarded as a non-aqueous diluent. Again, an extraneous non-aqueousmaterial such as methyl alcohol or ethyl alcohol may be added, to thereaction mass to serve as a non-aqueous diluent.

A particularly important phase of my invention is based upon thediscovery that methyl alcohol.

a temperature not substantially exceeding +10 degrees C., and preferablyfalling within the range of about --'l0 degrees C. to +10 degrees 0.,the undesired alkylation of the monoethanol- In my copendingapplication, above identified,

I have disclosed the following compoundaar'nbng others, which werewithin the scope of my invention therein claimed, and it will beclear-that said compounds and others may be produced in 04) accordancewith my novel teachings herein. ,mon (1) C H::C--CH2CHr-NHCOCHr-BOINI(25) CHH O .Q,H NH CO. .CHIC! (2) CnHu-(%O-CHr-C Hr-NH- -C O-CHr-501K(26) (2'1) CnHnCO-CzH|N-COCH:CI (3) CuHfl-G-O-CHz-CH:-NHCO-CHg-SOaNHAIHOH 1o (4) cflHPC-o-c2H4-NHC0-CHI-GHI-BO3NI (28) CuHrC-O-ONH-CO-CH2SO1Kl A g (W401i 2o c,1ns-c-o-'-o,m-o-c,n.-NH-o-cnr-soimC1H1sC-O-OHICH:NHC0-CH:SOa-NC:H&OH Y

. canon (30) c.H,'-C--0C,HiS-C=Hr-NH-C-CHCH: (6)CIIHfl-COCHICHCHINHCOCH:S0:K 01K H SOaNa M951 (31) CUHir-oo-mm-NE-C-QH-CH-cm CioHn-CO-CHa-CHr-NHCOCHr-BQ|.N H (0171) ONB H 32)Charo-o-mm-rm-c-cn-cm-o-o0:11 (s) CuHu-OCHa-CHr-NH-CO-=CH:B0:. 01K

- H In general, as indicated hereinabove, the com- (9)CnHzr-C-O-CHz-CHz-Cliz-NH-CO-GHz-SOLNHl u s a e p p ed. i ac orda e withthe 1 present invention, by initially reacting an alcohol primary orsecondary amine or, in other (10) 01114011 words, alcohol or alkylolnon-tertiary amine, in-

CnUn-C-O-CHr-CHa-NH-C OCH2SOa.N -C;H|OH eluding corresponding alkylolpolyamines, with a CQHOH lower molecular weight alcohol ester of a lowermolecular weight halogeno-carboxylic acid, the (11)Clix-(CH1)rCHfi-OCH:-CB2NHCO-CHr-SOaNa 3!- reaction being conducted in anon aqueous m H 0 dium and the alcohol ester being preferably in excess,the conditions being such as to insure (12) fia substantial yield ofamide. The alcohol ester should best be that derived from a volatilealcohol such as methyl alcohol or ethyl alcohol but, as indicatedhereinabove, methyl alcohol esters so K of halogeno-acetic acid,particularly methyl E chloracetate, are outstandingly useful, espe- 0cially when the amidification reaction with H OCH monoethanolamine orthe like is conducted. at low temperatures, preferably between about(14) E10 CH-(fi-WCHI'CHTNH'CDam-501M 10 degrees C. and about +10 degreesC. The

moon: 0 resulting amide, preferably after certain purification steps, isreacted, ,as described in my who}; aforementioned copending application,with (1 clinn-c-o-cla'i-clih-l mco-cm-sOtis-01114011 preferably a highermolecular weight organic.

" H acid halide, anhydride or other agent or com- CHOH bination ofagents, for example, mixtures of 2 higher fatty acids with thionylhalides such as (16) CoHrC-0GHzGH:-Nn-c0-cH2-S0=.N0i thionyl chloride,or mixtures of higher fatty acids 1 50 with phosphorus halides such asphosphorus trichloride or phosphorus pentachloride, to in- (17)Qumra-Cm-CHrNH-cFem-501K troduce a higher acyl radical into the molecule(13 CsHn0CHz-CH:-NHC 0-CHr-SO3N8 whereby to produce an ester of theamide, and

with an alkali sulphite for example sodium po- 0 H o-oon on CH NH-CO-CHCH SOK (19) r r o r r a tassium, ammonium, or lithium sulphite, tointroduce a sulphonic group into the molecule. An alternative method,although not, in general, quite as satisfactory as my preferred methodsdescribed generally hereinabove, comprises 02H: initially producing analcohol ester of a sulpho- 21GHr-(CHI)1-CHCl-CHCl(CHa)1-C-0CHeCHr-NHCO-GH:SO3K

I/CZHI (22) CuHrC-OCH:CH:-OCHQCH:NH-CO-GHs-SOmN-Csfll ried outpreferably at temperatures of the order of 100 degrees C. or somewhathigher but below the'decomposition temperature of either of the reactingconstituents or the desired product, and with vigorous mixing orkneading.

The following examples are illustrative of the (4) 435grams of thereaction product of part (3) hereof were added to 3 liters of isopropylalcohol and the mixture was heated to boiling,

with stirring, the mass then being filtered, while hot, in order toremove inorganic salts, and the alcohol filtrate was allowed to cool toroom temperature whereupon a crystalline material separated out. Thecrystalline material was separated from the solution by filtering andthe crystals were washed with a small amount of ether and thenair-dried. The finally obtained crystals were white, had good foamingproperties and novel methods which have been described generallyhereinabove for preparing variousof the compounds which I disclosed inmy aforementioned copending application. It will be appreciated thatvariations may be made in the procedure described in said examples, forinstance, by varying the proportions of reacting constituents, times ofreaction, temperatures. and the I like, and various supplementaryprocesses of purification may be resorted to wherever found desirableorconvenient. These and other variations and modifications will beevident to those skilled in the art in the light of the guidingprinciples which are disclosed herein.

Example A (1) To 217 grams (2 mols) of methyl chlor-- acetate 62 grams(1 mol) of monoethanolamine were added slowly with stirring, thetemperature of the mixture being keptat approximately'o degrees C. Theaddition of the monoethanolamine was made over a period of about 1%hours, a small amount of finely divided solid carbon dioxide being addedto the reaction product to help maintain the temperature at about 0degrees C. The reaction product was then subjected to a vacuum at atemperature of 20 degrees' C. to degrees C. and at an absolute pressureof 12 mm. to '70 mm. in. order to remove the methyl alcohol which formedduring the reaction, the carbon dioxide, and at least most of the excessmethyl ch1oracetate. Approximately 180 grams of a reaction product wasobtained consisting essentially of the chloracetamide ofmonoethanolamine v of, 330 grams of lauroyl chloride (approximately 63%vpure, the balance comprising largely lauric acid) were added and themass was heated, with stirring and under vacuum, for. one hour at atemperature, ranging from degrees C. to 95 degrees C. in order to removethe hydrochloric acid which formed during the reaction. The reactionmass was then washed four times with tap water at 65 degrees C. untilfree of hydrochloric acid.

(3) To the reaction product of part (2) hereothe reaction product ofpart (1) here'- comprised essentially a compound having the followingformula:

cnnii-s-o-cgm-Nn-o c-om-s oak If desired, instead of purifying thecompound to remove the inorganic salts, said salts may be permitted toremain. However, the isop'ropyl al-.

cohol or other solvent should still preferably be employed in order toremove unreacted or free fatty acids or soaps which may be present, suchfatty materials, in general, interfering with the foaming properties ofthe desired product. It

will be understood that I prefer to purify the product in order toobtainthe best results, but, if desired, the product may be used in the formof the impure reaction mixture.

(5) In order to convert the potassium salt of the compound of part (4)hereof into an alkylolamine salt, alkylolamine salts of such compoundsbeing particularly preferred for certain purposes,

the following procedure was carried out? 432 grams of the lauric acidester of the sulphoacetic acid amide of monoethanolamine (potassiumsalt), corresponding to the formula:-

c.;n,i-o-o-c,n.-Nn-- cm-s 03K o were dissolved in 1483 grams of water,at 60 degrees C. and there was added thereto, with stirring, a solutionof 213 grams of tartaric acid in 213 cc. of water. There was then addedthereofthere-was added a solution containing 53.2

grams of potassium meta bisulphite; 26.8 grams of potassium hydroxideand 160 cc. of water and the mixture was heated, with stirring. forapproximately of an hour to an hour at a temperature ranging fromdegrees C. to 95 desrees C. I

to, with vigorous stirring, a solution of 88 grams of monoethanolaminein 88 cc. of "water. The final product was cooled to about 20 degrees C.to 22 degrees C. and filtered to remove the precipitate of potassiumacid tartrate which formed during the reaction. To the clear, limpidfiltrate,

11 cc. of monoethanolamine were added in order to neutralize thesolution to a pH of about 6.0. The solution contained a substantialproportion of ,the monoethanolamine salt of the sulphoacetic acid amideof the lauric acid ester of monoethanolamine, said compound having thefollowing formula:

The solution had excellent foaming and deter-' cc. by the additionthereto of water and there were then added thereto, with stirring. 1150cc.

- of an aqueous solution containing 40% monoethanolamine sulphate,namely, the sulphuric acid salt of monoethanolamine. The final productwas a clear, viscous material which was very satisfactory as a shampoobase.

of methyl chlor'acetate to monoethanolamine of about 1.5 to 1 to about 2to 1 is preferred, the latter molal ratio representing close to theoptimum operating conditions.

It should also be understood that the use of solid carbon dioxide may beomitted and, if desired, oxalic acid may be employed to precipitateexcess monoethanolamine should the reactionbe carried out in such amanner that excess monoethanolamine is present. This, however, does notrepresent the preferred embodiment of the invention.

Example B (1) 108.5 grams of methyl chlor acetate were dissolved in 327grams of methyl alcohol and there were added thereto, slowly and withstirring, 74.4 grams of monoethanolamine. The reaction mixture wasmaintained at a temperature of about degrees C. for approximately 1%hours. The temperature was then allowed to rise over a period of about 1hour to +10 degrees C. at which stage the amidification reaction wasapproximately 98% complete. The slight excess of monoethanolamine wasthen removed by,

adding slowly, and with stirring, 17.32 grams of oxalic acid dissolvedin cc. of methyl alcohol. The precipitated oxalic acid salt ofmonoethanolamine was then filtered of! and the methyl 121- l cohol wasevaporated oil under vacuum from the filtrate. At room temperature, thereaction product was a viscous, pale straw to amber colored l liquid andconsisted essentially of the chloracetamide of monoethanolamine.

(2) 124 grams of the reaction product of part (1) hereof were, mixedwith 176.5 grams of 90% pure lauroyl chloride and the mixture washeated,

. with stirring and under vacuum, for 1 hour at about degrees C. untilno more hydrochloric acid was driven off. The reaction mass was thenwashed twice, each time with 4 liters of water at 60 degrees C. untilthe wash water was free of hydrochloric acid.

(3) 150 grams of the reaction product of part (2) hereof were. added toa solution of grams of sodium sulphite in 500 cc. of water and the masswas stirred at a temperature of 95 degrees C. to 98 degreesC. forapproxlmatelyan hour, the chlorine splitting oil. and being replaced bythe group SChNa. The resulting product consisted essentially of acompound having the formula mixed with inorganic salts such as sodiumchloride. If desired, the product may be purified as described inExample A herelnabove.

Instead of washing the reaction product of part 2) hereof in order torid the same of hydrochlor- I Example C (1) 244 grams of ethylchloracetate were stirred for four hours at 25 degrees C.-30 degrees C.with a solution made of 266 grams of potassium metabisulphite, 133 gramsof potassium hydroxide and 800 cc. of water. The reaction mixture wasthen chilled in an ice bath and so maintained for about 2 hours and theresulting crystalline mass was filtered by suction. Approximately 195grams of a crystalline reaction product were obtained consistingessentially of ethyl sulphoacetate, potassium salt. This reactionproduct contained about 3% of potassium chloride and the filtrate wasconcentrated by blowing air over the surface thereof and a second cropof crystals, amountin to grams, was obtained, said crystals beingilltered off. This batch of crystals also contained approximately 3%potassium chloride. If desired, the mother liquor may again beconcentrated to obtain further batches of crystals but it is preferrednot to continue with repeated crystallization since the productbecomestoo much concentrated with potassium chloride.

(2) 108 grams of the ethyl sulphoacetate, po-

tassium salt, produced in accordance with part (1) hereof, werethoroughly mixed with 31 grams of monoethanolamine and the mixture washeated for 8 hours at 100-110 degrees C. During the period of heating,it was thoroughly mixed or kneaded. It was then allowed to remain in anoven at a temperature of 85'degrees C. to degrees C. for several hours.The final product comprised a solid, nearly white, hard case consistingessentially of a compound having the following formula:

Hocm,. m- ?-omso.x

. 112 grams of the product were obtained, the

theoretical yield being 114 grams. The product was then ground in amortar to pass through a sieve having 40 meshes to the linear inch.

(3) grams of the reaction product of part (2) hereof and 73 grams oflauroylchloride (containing 75% lauroyl chloride, the balance comprisinglargely lauric acid) were mixed together and evacuated in order to drawoff the hydrochloric acid which formed during-the reaction period. Themixture was heated on a water bath for a period of 6 hours at atemperature between 75 degrees C. and 85 degrees C., the mass beingconstantly mixed during the heating period in order to break up thelumps of the product. The final product, when ground, was a nearly whitepowder consisting essentially of a compound having the formula Theproduct may be purified, if desired, by extraction with ethylenedichloride, ether or other fat-solvents.

Example D which formed during the reaction and the excess methylchloracetate were distilled off in vacuo at a temperature of" about-60degrees C. The reaction product contained a substantial proportion ofthe chloracetarnide of diethanolamine.

(2) 'To 94 grams-of the reaction product of part (1) hereof there wereadded dropwise and with stirring 99 grams of lauroyl chloride, the

addition being made over a period of about 20 minutes and-whilemaintaining the reaction mass at a temperature ranging from 80 degreesC. to 100 degrees C. The final reaction product was a clear, lightamber, semi-viscous material containing a substantial proportion of acompound ing 81.5 grams of KzSsOs, 69.7 grams of KOH,

and 276 cc. of water, the mixture being stirred and heated for about onehour at a temperature ranging from 65 degrees C. to 90 degrees C. Thereaction product contained a substantial proportion of a compound havingthe following probable formula:

(4) The reaction product of part (3) hereof was purified by addingthereto 3600 cc. of isopropyl alcohol containing 41 cc. of concentratedhydrochloric acid previously heated to 50 degrees C. The mixture wasthen stirred and heated to 80 degrees C. and the inorganic salts wereill tered oil. The filtrate was then cooled to room temperature in acold water bath, 1000 cc. of isopropyl alcohol were added to saidsolution and the precipitate which formed was then filtered off. 'Iiheprecipitate comprised a thick, white paste which had good foaming,wetting, detergent and surface modifying properties. It comprisedessentially the sulpho-"acetamide of the mono-lauric acid ester ofdiethanolamina' having the formula set out hereinabove under part (3).

Example E phite, as described in part (3) of Example A hereinabove. Theresulting reaction product contained a substantial proportion of thelauric acid ester of the sulpho-acetamide of monoethanolamine which hadproperties of the character described in the previous examples.

It will be understood that the novel processes of my present inventionmay be employed for producing any of the novel compounds which Ihave-disclosed in my aforementioned copending application.

As described in saidcopending application, the organic radicalrepresented by R in the general formulae may be derived from varioussources. Among such sources may be mentioned straight chain and branchedchain carboxylic, aliphatic, and fatty acids, saturated and unsaturated,such as butyric acid, caprylic acid, caproic acid, capric acid, sebacicacid, behenic acid, arachidic acid, cerotic acid, erucic acid, melissicacid, stearic acid, oleic acid, ricinoleic acid, linoleic acid,linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures ofany two or more of the above mentioned acids or other acids, mixedhigher fatty acids derived from animal or vegetable sources, forexample, lard, coconut oil,- rapeseed oil, sesame oil, palm kernel oil,palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow,

.soya bean oil, peanut oil, castor oil, seal oils,

whale oil, shark oil, partially or completely hydrqgenated animal andvegetable oils such as those mentioned; hydroxy and alpha-hydroxydegrees C. The mixture was then heated to 90 degrees C. and maintainedat that temperature for twenty minutes, hydrochloric acid gas andsulphur dioxide gas, which formed during the reaction, being permittedto escape. To the resulting reaction mass there were then added 55 gramsof thionyl chloride, the addition being gradual and with stirring over aperiod of about 10 minutes. The resulting mixture was then heated to 90degrees C. and maintained at that temperature for about 20 minutes, theexcess thionyl chloride then being removed in vacuo.

(2) The reaction product of part (1) hereof was then reacted withpotassium meta-bisulhigher aliphatic and fatty acids such as i-hydroxystearic acid, dihydroxy stearic acid, alphahydroxy stearic acid,alpha-hydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxycoconut oil mixed fatty acids, and the like; fatty acids derived fromvarious waxes such as beeswax, spermaceti, montan wax, and carnauba waxand carboxylic acids derived, by oxidation and other methods, frompetroleum; cycloaliphatic and hydroaromatic acids such ashexahydrobenzoic acid, resinic acids, naphthenic acid and abletic acid;aromatic acids such as phthalic acid, benzoic acid, naphthoic acid,pyridine carboxylic acids; hydroxyaromatic acids such as salicylic acid,hydroxy benzoic and naphthoic acids, and the like; and substitution andaddition derivatives of the aforementioned carboxylic substances. Itwill be understood that mixtures of any two or more of said acids may beemployed if desired. These acids are utilized especially in the form oftheir acyi halides.

The halogeno-carboxylic acids which, in the form of their esters,particularly with methyl alcohol, are reacted with the alcohol oralkylol pri- .,mary and secondary amines may be selected from arelatively large class including mono-, di-, and poly-carboxylicderivatives as, for example, mono chloracetic acid, mono bromaceticacid, mono iodo acetic acid, alpha-chlor propionic acid, alpha-brompropionic acid, alpha-chlor butyric acid, alpha-bromo capric acid, monochlor succinic acid, dichlor succinic acid, di chlor, glutaric acid, andthe like. Of special utility, as previously indicated, are methylalcohol esters of the halogeno acetic acids, particularly, methyl chloracetate.

The alcohols whose halogeno-carboxylic esters are reactedwith thealcohol primary and secondary amines are preferably of lower molecularweight, especially the volatile alcohols, namely, methyl alcohol andethyl alcohol, being preferred with the methylalcohol being especiallydesirable when utilized under the conditions described heleinabove. Itwill be understood that the re- .activity of the alcohol esters of thehalogeno carboxylic acids or of the sulpho-carboxylic acids 'inconnection with the formation of the amides therefrom withmonoethanolamine or the like is dependent upon the alcohol portion ofthe ester molecule as well as upon the halogeno carboxylic'diethanolamine, monopropanolamine, di-propanolamine, monobutanolamine,ethyl monoethanolamine, the mono ethyl ether of diethanolamine,mono-cyclohexyl, beta-hydroxy-ethyl amine; monobutyl, beta-hydroxyethylamine; ethanol aniline; l-arrnno-propanediol-2,3; glycerol and otherpolyhydric alcohol and sugar or sugar alcohol primary and secondaryamines such as glycerol mono amine, sorbitol mono amine, mannitol monoamine, and the like. As indicated hereinabove, monoethanolamine isespecially satisfactory in carrying out the novel processes of thepresent invention.

Wherever the term higher" is employed as referring to higher molecularweight organic or fatty acids or the like, it'will beunderstood to covercompounds or radicals having at least six carbon atoms, unless otherwisespecifically stated.

Wherever the term sulphonic group, sulphonic radical, sulp'noacetamide'or like expression isemployed in the claims, it will beunderstood to refer to the compounds irrespective of whether thehydrogen of the sulphonlc acid radical is present as such or replaced byanother cation, unless the connotation otherwise expressly indicatesdifferently.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. The method of preparing chemical compounds which comprises reactingan ester of a halogeno-carboxylic acid with an alcohol nontertiary amineto form an amide, said reaction beingconducted in a substantiallynon-aqueous medium, and then introducing into the amide (l) a sulphonicgroup and (2) an organic radical containing from eight to eighteencarbon atoms.

2. The method of preparing chemical compounds which compflses reacting amethyl alcohol ester of a member selected from the group consisting ofchloracetic acid, bromacetic acid and iodo acetic acid, with an alkylolnon-tertiary amine to form an amide. said reaction be ing carried out ata temperature of the order of -l degrees C. to degrees C., and thenintroducing into said amide (l) asulphonic group and (2) a fatty acidradical containing from eight to eighteencarbon atoms.

3. The method of claim 2 wherein the alkylolamine comprises a member ofthe group consisting of monoethanolamine, diethanolamine and mixturesthereof.

4. The method of claim'2 wherein the sulphonic group is introduced intothe molecule subsequent to the introduction into the molecule of saidfatty acid radical.

5. The process of preparing chemical compounds which comprises reactingthe methyl ester of chloracetlc acid with monoethanolamine, in asubstantially non-aqueous medium, at temperatures of about 10 degrees C.to about +10 degrees C. to produce essentially N -beta-hydroxyethyl,chlor-acetamlde, then reacting said amide with a fatty acid acyl halidecontaining from eight to eighteen carbon atoms to produce thecorresponding fatty acid ester of said amide, and then reacting saidcompound with an alkali metal sulphite whereby the chlorine group of thefatty acid ester of the N-beta-hydroxyethyl, chloracetamide is replacedby a sulphonic group.

6. The process of preparing chemical compounds which comprises reactingat least one mol of the methyl 'esterot chloracetic acid with one moi ofa mono-alkylolamine at a' low temperature to produce essentially thechloracetamide of the monoalkylolamine, then reacting said amide with afatty acid acyl halide containing from eight to eighteen carbon atomstoproduce the corresponding ester or said amide, and then reacting saidcompound with an alkali metal sulphlte whereby the chlorine group of theester of the amide is replaced by a sulphonic group.

'I. The process of preparing chemical compounds which includes the stepsof reacting the methyl ester of chloracetic acid with monoethanolamine,in a substantially non-aqueous medium, at'temperatures of about -10degrees C. to +10 degrees C. to produce essentially N-beta-hydroxyethyl, chloracetamide, distilling of! methyl alcohol whichforms during the reaction andsuch unreacted methyl chloracetate whichmay be present, reacting the N-beta-hydroxyethyl, chloracetamide to forma higher molecular ,weight fatty acid ester thereof, and then reactingsaid ester with an aqueous solution 0! an alkali metal sulphite wherebythe chlorine group of 'the fatty acid ester of the N-beta-hydroxyethyl,chloracetamide is replaced by a sulphonic group.

8. The method of preparing chemical com-. pounds 'which includes thestep of reacting monoethanolamine with an excess or a stoichiometricequivalent amount of methyl chloracetate, in a substantially non-aqueousmedium, at a temperature between about -10 degrees C. and

+10 degrees C. to convert the monoethanolamine into N-beta-hydroxyethyl,chloracetamide.

9. The method 01' preparing chemical compounds which include: the stepof reacting an alkylol non-tertiary amine with a methyl ester of -ahalogeno-acctic acid, in a substantially non- .aqueous medium, at atemperature sumciently low to avoid appreciable alkylation of thealkylolamine but effective to produce high yields of thehalogeno-acetamide oi the alkylolamine.

10. The method of preparing chemical compounds which includes the stepof reacting monoethanolamine with methyl chloracetate. in asubstantially non-aqueous medium, at a temperature between about -10degrees C, and about +10 degrees C. to convert the monoethanolamine intoN-beta-hydroxyethyl, chloracetamlde.

11. The method of preparing chemical compounds which includes the stepof reacting a monoalkylolamine with a methyl ester of a halogeno-aceticacid, in a substantially nonaqueous medium, at a' temperature notsubstantially above +10 degrees C. to convert the monoalkylolamine intothe halogeno-acetarnide thereof.

12. The method of preparing chemical comc eater 4 pound with an alkalimetal sulphite whereby the pounds which includes the step of reacting amono-alkylolamine with methyl chloracetate, in a substantiallynon-aqueous medium, at a temperature between about --10 degrees C. andabout +10 degrees C. to convert the mono-alkylolemine into thechloracetamide thereof.

13. The method of preparing chemical compounds which includes the stepof reacting monoethanolamine with a methyl ester of a halogenoaceticacid, in a substantially non-aqueous medium at a temperature betweenabout -10 degrees C. and about +10 degrees C. to convert themonoethanolamine into N-beta-hydroxyethyl, halogeno-acetamide. 7

1d. The method of preparing chemical compounds which includes the stepof reacting monoethanolamine with methyl chloracetate, in a sub--stantially non-aqueous medium, at a temperature between about l degreesC. and about +10 degrees C. to convert the monoethanolamine into'N-beta-hydroxyethyl, chloracetamide, and then introducing into saidN-beta-hydroxethyl, chloracetamide a sulphonic group and an organicradical containing at least four carbon atoms.

15. The process of preparing chemical compounds which comprisesreacting, in a substantially non-aqueous medium, a lower molecularweight alcohol ester 01' a lower molecular weight halogeno-carboxylicacid with an allgvlol nontertiary amine to produce essentially ahalogenocarbomlic acid amide of the alkylolamine, then,

reacting said amide with, an acyl halide containing at least four carbonatoms to produce the corresponding ester or said amide, and thenreacting said compound with an alkali metal sulphite whereby thechlorine group of the ester of the amide is replaced by a sulphonicgroup.

16. The method of preparing chemical compounds which comprises reacting,in a substantially non aqueous medium, a lower molecular weight alcoholester of a member selected from the group consisting of chloraceticacid, bromacetic acid, and iodo acetic acid, with an alkylolnon-tertiary amine to form an amide, and then introducing, at oppositeends oi the amide, (1) 4 a fatty acid radical containing at least fourcarbon atoms and (2) a sulphonic group.

17. The method 01 claim 16 wherein the al-v kylolamine comprises amember' or the group consisting oi monoethanolamine, diethanolamine. andes thereof.

18. The process of preparing chemical compounds which comprises reactingthe methyl ester of chloracetic acid with monoethanolamine, in asubstantially non-aqueous medium, at temperatures of about -10 degreesC. to about +10 deselected from the group consisting of salts of'halogeno-acetic acid and sulpho-acetic acids, in

chlorine] group of the. lauric acid ester of the N-beta-hydroxyethyl,chloracetamide is replaced by a sulphonic group; I

19. The method of preparing chemical compounds which comprises reactingethyl sulphoacetate with monoethanolamine, in a substantiallynon-aqueous medium, at elevated tempera? tures while mixing-or kneadingthe reaction mass, to form the sulpho-acetamide of monoethanolamine, andthen esterifying said amide by reacting it with a fatty acid acyl halidehaving from eight to eighteen carbon atoms.

20. The method of preparing chemical compounds which comprises reactingethyl sulphoacetate with an aikylol non-tertiary amine, in asubstantially non-aqueous medium, to form a v sulphc-acetamide of thealkylolamine, and then reacting said amide with a carboxylic acylhalide.

containing at least four carbon atoms.

21. The method of claim 20 wherein the .al-

kylolaminecomprises a member of the group consisting ofmonoethanolamine, diethanoiamine,

' and mixtures thereof.

22. The method of preparing chemical compounds which comprises reactingethyl sulphuacetate mm monoethanolamine, in a substantially non-aqueousmedium, to form a sulphoacetamide of monoethanolatnine, and thenreacting said'amide with afatty acid acyl halide having from eight toeighteen carbon atoms.

23. The method oi preparing chemical compounds which comprises reacting.a volatile alcohol ester of a lowermolecular weight sulphocarboxylicacid with an allwlol non-tertiary amine, in a substantially non-aqueousmedium,

to form a sulpho-carboxylic acid amide of the allgvlolamine, and thenreacting said amide with an acyl halide containing at least four carbonatoms.

24."T1 1e method of preparing chemical com pounds which comprisesreacting monoethanol-= amine with a methyl alcohol ester of a member asubstantially non-aqueous medium, to form amides of monoethanolamine,and then reacting said amides with a. fatty acid acyl halide contain-'ing from eight to eighteen carbon atoms.

25. The method of preparing chemical compounds which comprises reactingan alkylol nontertiary amine with a volatile alcohol ester 01 a areas 0.to produce essentially N-beta-hydroxymember selected from the groupconsisting of salts of lower molecular weight halogeno-carboxylic andsulphocarboxylic acids, in a substantially non-aqueous medium, .to formamides of said alkylolamine, and then reacting said amides with acarboxylic acyl .halide containing from eight to eighteen carbon atoms.

isomers B. KA'rzMAn.

